1. Field of the Invention
This invention relates to a copolymer excelling in dispersing ability of pigments, in particular, dispersibility of organic pigment such as diketopyrrolopyrrole; to a pigment dispersion in which said copolymer is used; and to a paint composition containing said pigment dispersion, which excels in stable color development.
2. Description of the Invention
Pigment dispersion pastes which are formed by dispersing pigment in a mixture of a dispersing resin, solvent and if necessary a dispersion promotor, have been widely used for paints and inks for coloring. In the field of paints and inks, social needs require further improvements in such properties as color developing ability and sharpness with increasing keenness, in addition to better performance of the paint film or printed matter per s. To meet the requirements, various organic pigments such as phthalocyanine pigments, quinacridone pigments, diketopyrrolopyrrole pigments and the like have been developed.
Whereas, even when a new pigment having excellent color developing property or sharpness meeting the social demands is developed, a dispersing resin and dispersion promotor matching the pigment must be used for preparing a dispersion showing the original innate color of the same pigment. The pigment dispersion, furthermore, must have sufficient stability to prevent reagglomeration of pigment particles, when it is used in a paint or ink. Hence, proposals have been made to develop dispersing resins and/or dispersion promotors which exhibit excellent pigment dispersibility, capacity for drawing forth the maximum color developing property of the available pigment and also excellent pigment dispersing stability to effectively inhibit re-agglomeration of the pigment particles in the formed pigment dispersion.
Such past proposals include, for example, (1) method of using a lubricant such as nonionic, cationic or anionic surfactant as the dispersion promotor (cf U.K. Patent Nos. 1108261 and 1159252), (2) method of using a pigment derivative as the dispersion promotor, which is mixed with a pigment to disperse the latter [cf. Sho 51(1976)-18736A1-JP], (3) method of using a nitrogen-containing compound as the dispersion promoter and a polyester oligomer as the dispersing resin, to improve dispersibility of the pigment and stability of the pigment dispersion by utilizing the affinity between the polyester oligomer and the nitrogen-containing compound [cf. Sho 58(1983)-145762A1-JP], (4) method of using a pigment dispersing agent comprising a component to form a steric repelling layer composed of a pigment-adsorbing component having nitrogen-containing substituent groups and polyester resin [cf. Hei 4(1992)-352882A1-JP] and (5) a method of using a copolymer which is obtained from a monomer having tertiary amino group and/or quaternary ammonium base and a polyalkyl (meth)acrylate macromonomer having a (meth)acryloyl group at its terminal [cf. Hei 8(1996)-253540A1-JP].
Where the dispersion promoter in the above method (1) is used, however, the adsorption layer adsorbed onto the particle surfaces is too thin to exhibit satisfactory stabilization effect, and no appreciable improvement in pigment dispersibility is achieved. In the above method (2), the pigment derivatives used are themselves essentially colored, and hence this method cannot be generally used for all pigments. In the method (3), the polyester oligomer used therein has poor compatibility with acrylic resins which are of particular importance as resins for paint. In consequence, it is difficult for this method to attain in acrylic resin-derived paints the color developing property inherent in individual pigments. Furthermore, although the methods (4) and (5) introduced a steric repelling component, adsorption of the dispersant onto pigment is insufficient and stability of pigment dispersion is unsatisfactory. In particular, in the occasion of dispersing diketopyrrolopyrrole pigments, the insufficient adsorption of the dispersant onto the pigments causes notably inferior color developing property and dispersing stability. An attempt was made to give a surface treatment to the pigment with the view to improve said defect, which, however, achieved neither any substantial improvement in dispersing stability of the pigment nor full exhibition of innate color-developing property. Where the pigment concentration was high, furthermore, troubles were caused by the surface treating agent of the pigment.
Thus, the main object of the present invention is to provide a pigment dispersion which excels in dispersibility and dispersion stability of a broad range of pigments, in particular, in those of difficulty dispersible pigments such as diketopyrrolopyrrole pigments, and is capable of drawing forth the innate color developing ability of individual pigments; dispersing resin useful for preparation of such a pigment dispersion; and also a paint composition using the pigment dispersion, which excels in color developing ability and appearance of the coat film.
This invention provides a copolymer which is characterized in that said copolymer is obtained through copolymerization of
(a) carboxyl-containing, polymerizable unsaturated macromonomer 5-50 parts by weight,
(b) at least one polymerizable unsaturated macromonomer selected from polyalkyl (meth)acrylate macromonomers and polystyrene macromonomers 30-70 parts by weight, and
(c) at least one other polymerizable unsaturated monomer which is co-polymerizable with above (a) and/or (b) component 5-65 parts by weight, said copolymer having a number-average molecular weight within a range of 2,000-100,000 and a resin acid value within a range of 10-200 mgKOH/g.
The invention also provides a pigment dispersion which contains said copolymer, pigment, organic solvent and optionally a dispersion promotor.
The invention furthermore provides a paint composition containing said paint dispersion.
Hereinafter the invention is explained in further details.
A copolymer according to the invention is prepared by copolymerization of a carboxyl-containing macromonomer (a), a specific macromonomer (b) and other polymerizable unsaturated monomeric component (c), which are hereafter explained.
Carboxyl-containing Polymerizable Unsaturated Macromonomer (a):
The carboxyl-containing, polymerizable unsaturated macromonomer, which serves as the component (a) constituting a copolymer of the present invention, has at least one carboxyl group and at least one polymerizable unsaturated bond per molecule. This monomeric component is useful when said copolymer of the invention is used for dispersing pigment, for effectively adsorbing the copolymer onto the pigment. Because the component (a) is in the form of a macromonomer, it can assist localization of the pigment-adsorbing component in the copolymer of the invention, whereby improving the adsorbing ability of the copolymer to the pigment and preventing re-aggromeration of the pigment, to improve stability of the pigment dispersion.
The carboxyl-containing, polymerizable unsaturated macromonomer (a) can be prepared by a production method known per se, for example, by a process comprising synthesizing in advance a vinyl polymer having a carboxyl precursor group which is convertible to a carboxyl group by a post-treatment, and treating the vinyl polymer to introduce thereinto a polymerizable, unsaturated group and convert the carboxyl precursor group to a carboxyl group. More specifically, for example a carboxyl-containing macromonomer can be prepared through the steps of copolymerizing a monomeric mixture of tert-butyl (meth)acrylate and other vinyl monomer using a carboxyl-containing chain transfer agent represented by 3-mercaptopropionic acid and if necessary a radical polymerization initiator, in the presence of an organic solvent, to form a copolymer with carboxyl group-terminated polymer chain; reacting the resulting copolymer with an epoxy-containing monomer such as glycidyl methacrylate to introduce a polymerizable double bond to the copolymer chain terminal; and then adding to said copolymer, into which said polymerizable double bond has been introduced, an acid catalyst such as p-toluenesulfonic acid and heating the system to decompose the tert-butyl ester group and convert it to carboxyl group.
In this specification, xe2x80x9c(meth)acrylatexe2x80x9d signifies xe2x80x9cacrylatexe2x80x9d or xe2x80x9cmethacrylatexe2x80x9d.
Such carboxyl-containing, polymerizable unsaturated macromonomer (a) normally conveniently has a number-average molecular weight within a range of 500-15,000, in particular, 600-10,000, for effective localization of pigment-adsorption groups and ease of production. The macromonomer (a) furthermore conveniently has an acid value within a range of 20-400 mgKOH/g, preferably 25-300 mgKOH/g, for improvement in dispersibility brought about by adsorption onto the pigment used and better solubility and moisture resistance of the macromonomer. The macromonomer (a) preferably is linear, and has a polymerizable double bond or bonds on at least one terminal, preferably at one terminal, of its polymer chain.
Polymerizable Unsaturated Macromonomer (b);
The polymerizable unsaturated macromonomer which serves as the component (b) constituting the copolymer of the present invention is at least one macromonomer selected from the group consisting of polyalkyl (meth)acrylate macromonomer and polystyrene macromonomer having a polymerizable unsaturated bond on at least one of the terminals of the polymer chain.
Said polyalkyl (meth)acrylate macromonomer has, as the main chain, a (co)polymer of an alkyl ester of acrylic acid or methacrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate and the like; preferably (co)polymers of acrylic acid or methacrylic acid alkyl esters containing C1-C24 alkyl group.
Such a polyalkyl (meth)acrylate macromonomer can be prepared, for example, through the steps comprising copolymerizing an alkyl ester, or a mixture of alkyl esters, of acrylic acid or methacrylic acid as named above, using a carboxyl-containing chain transfer agent represented by 3-mercaptopropionic acid and if necessary a radical polymerization initiator, in the presence of an organic solvent, to form a copolymer having terminal carboxyl group or groups; and reacting the copolymer with an epoxy-containing, polymerizable unsaturated monomer such as glcidyl methacrylate, whereby introducing a polymerizable double bond or bonds to a terminal or both terminals of the copolymer chain by reacting the carboxyl group(s) with the epoxy group(s).
Said polystyrene macromonomer can be obtained, for example, through the steps of copolymerizing styrene using a carboxyl-containing chain transfer agent represented by 3-mercaptopropionic acid and, if necessary, a radical polymerization initiator, in the presence of an organic solvent, to form a carboxyl group-terminated copolymer; and reacting the same copolymer with an epoxy-containing polymerizable unsaturated monomer such as glycidyl methacrylate, whereby introducing a polymerizable double bond or bonds into the copolymer chain terminal or terminals by the reaction between the carboxyl group(s) and epoxy group(s).
In the copolymer according to the invention, the polymerizable unsaturated macromonomer (b) forms a steric repelling layer differently from aforesaid carboxyl-containing polymerizable unsaturated macromonomer (a) which is the pigment-adsorbing component, and functions to prevent reagglomeration of the pigment. It is normally preferred for the macromonomer (b) to have a number-average molecular weight within a range of 1,000-15,000, in particular, 1,200-10,000 for ready formation of said steric repelling layer, stability of the pigment dispersion containing the copolymer and easy preparation of the macromonomer (b).
Such macromonomers (b) are commercially available, examples of which include MACROMONOMER AA-6 (a polymethyl methacrylate with methacryloyl group-terminated polymer chain, having a number-average molecular weight of about 6,000), MACROMONOMER AW-6 (a polyisobutyl methacrylate with methacryloyl group-terminated polymer chain, having a number-average molecular weight of about 6,000), MACROMONOMER AB-6 (a polybutyl methacrylate with methacryloyl group-terminated polymer chain, having a number-average molecular weight of about 6,000) and MACROMONOMER AS-6 (a polystyrene with methacryloyl group-terminated polymer chain, having a number-average molecular weight of about 6,000), which are products of Toagosei Ltd.).
Other Polymerizable Unsaturated Monomer(s) (c):
Other polymerizable unsaturated monomer(s) (c) which constitute the copolymer of the present invention with said carboxyl-containing macromonomer (a) having a high polarity and the macromonomer (b) as the dispersion-stabilizing component having a relatively low polarity, are not subject to any critical limitation as to their kind, so long as they are copolymerizable with macromonomer (c) and/or macromonomer (b).
Examples of other polymerizable unsaturated monomer (c) include: C2-C8 hydroxyalkyl esters of acrylic or methacrylic acid, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate; monoesters of polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol with polymerizable unsaturated carboxylic acids such as acrylic or methacrylic acid; adducts of hydroxyalkylvinyl ether, allyl alcohol, hydroxyalkyl ester of acrylic acid or methacrylic acid, (poly)alkyleneglycol mono(meth)acrylate or the like with lactones (e.g., xcex5-caprolactone, xcex4-valerolactone); monoethers of polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol with hydroxyl-containing unsaturated monomers such as 2-hydroxyethyl (meth)acrylate; adducts of xcex1,xcex2-unsaturated carboxylic acid with monoepoxy compound such as Cardura E10 (Shell Chemical Co., Ltd.) and xcex1-olefinepoxide; adducts of glycidyl (meth)acrylate and monobasic acid such as acetic acid, propionic acid, p-t-butylbenzoic acid and fatty acids; hydroxyl-containing unsaturated monomers such as hydroxyalkyl ethers like hydroxy-ethylvinyl ether, and hydroxyl-containing unsaturated monomer such as allyl alcohol; C2-C24 alkyl esters of acrylic acid or methacrylic acid such as ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate and stearyl (meth)acrylate; C2-C18 alkoxyalkyl esters of acrylic acid or methacrylic acid such as methoxyethyl (meth)acrylate and methoxybutyl (meth)acrylate; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, hexyl vinyl ether, cyclopentyl vinyl-ether, cyclohexyl vinyl ether and phenyl vinyl ether; allyl ethers such as allyl ethyl ether; vinyl esters such as vinyl acetate, vinyl butyrate, vinyl pivalate and Veoba monomer (Shell Chemical Co., Ltd.); propenyl esters such as isopropenyl acetate and isopropenyl propionate; olefinic compounds such as ethylene, propylene and butylene; vinylaromatic compounds such as styrene, xcex1-methylstyrene and vinyltoluene; (meth)acrylic acid esters of polyhydric alcohols such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,3-butylene di(meth)acrylate, 1,4-butanediol di(meth)acrylate, glycerine di(meth)acrylate, glycerine tri(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, neopentyl glycol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate; diallylisophthalate and divinyl benzene. These monomers can be used either singly or in combination of two or more.
Copolymer:
A copolymer of the invention can be prepared by copolymerizing a carboxyl-containing, polymerizable unsaturated macromonomer (a) which is an adsorbing component to pigment, polymerizable unsaturated macromonomer (b) which contributes to dispersion stability, and other polymerizable unsaturated monomer(s) (c). The copolymerization ratio of these components are within the following ranges, respectively, based on 100 parts by weight in total of these components, the parts being by weight,
component (a): 5-50 parts, preferably 10-45 parts, inter alia, 12-40 parts;
component (b): 30-70 parts, preferably 35-60 parts, inter alia, 38-58 parts;
component (c): 5-65 parts, preferably 5-55 parts, inter alia, 10-50 parts.
Copolymerization of above components (a), (b) and (c) can be normally performed by reacting them in an organic solvent and in the presence of about 0.01xe2x80x94about 10 parts by weight per 100 parts by weight in total of the components (a), (b) and (c) of a polymerization initiator, at a temperature within a range from about xe2x88x9220xc2x0 C. to about 160xc2x0 C. under normal or optionally under an elevated pressure up to about 30 kg/cm2G. Useful organic solvent is not critical, so long as it can dissolve or disperse above components (a), (b) and (c) and the copolymer obtained upon copolymerization of these components. More specifically, examples of usefuil organic solvent include: aromatic solvents such as xylene and toluene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate and 3-methoxybutyl acetate; and alcoholic solvents such as n-butanol and isopropyl alcohol.
As the polymerization initiator, any of those known per se as being useful for polymerization of polymerizable unsaturated monomers can be used. Typical examples include azo-type polymerization initiators such as 2,2xe2x80x2-azobisisobutyronitrile, aozbis-2-methylbutyronitrile and azobisdivarelonitrile; and organic peroxide-type polymerization initiators such as t-butyl peroxyisobutylate, t-butyl peroxy-2-ethylhexanoate, t-amyl peroxy-3,5,5-trimethylhexanoate, t-tubylperoxyisopropylcarbonate and 2,2-bis(4,4-di-t-butyl peroxycyclohexyl)propane.
The so obtained copolymers are considered to take well balanced comb structure formed of the carboxyl-containing macromonomer (a) unit which is a high polarity pigment adsorbing component, the macromonomer (b) unit which is a relatively low polarity dispersion-stabilizing component, and other polymerizable unsaturated monomer (c) units.
The copolymers of the present invention generally have a number-average molecular weight within a range from 2,000-100,000, preferably 3,000-50,000; and a resin acid value within a range from 10-200 mgKOH/g, preferably 15-150 mgKOH/g, for favorable pigment dispersion stability and ease of handling.
Pigment Dispersions:
A pigment dispersion according to the invention comprises above-described copolymer of the invention serving as a pigment-dispersing resin, pigment, organic solvent and if necessary a dispersion promotor, and further if necessary other additives.
Examples of pigment contemplated in the invention include: inorganic pigments such as titanium dioxide, zinc oxide, iron oxide, calcium carbonate, barium sulfate, chrome yellow, clay, talc and carbon black; and various organic pigments such as azo-, diazo-, condensation azo-, thioindigo-, indanthrone-, anthraquinone-, benzoimidazolone-, phthalocyanine-, isoindolinone-, perylene-, quinacridone-, dioxane-, and diketopyrrolopyrrole-type pigments. The copolymers of the present invention exhibit particularly remarkable pigment-dispersing ability and pigment dispersion stability as pigment-dispersing resin for diketopyrrolopyrrole pigments.
The organic solvent in such a pigment dispersion is not subject to any limitation, but any which can dissolve or disperse the copolymer may be used. For example, those organic solvents which are useful in the occasion of the copolymer preparation may be used.
Examples of the dispersion promotors, which are used if necessary, include wetting agents and as examples of still other additives, defoaming agent can be named.
The pigment dispersions of the invention are obtained by dispersing the named starting components with pigment by a method known per se. Examples of dispersing means for obtaining a pigment dispersion of the invention include: roll mill, ball mill, sand grind mill DCP mill, LMZ mill, attriter and paint shaker.
The use rate of the copolymer of the invention in preparation of the pigment dispersion is not critical. Generally, however, it is convenient to use it within a range of 5-300, in particular, of 10-200, parts per 100 parts of the pigment to be dispersed, parts being by weight.
Paint Composition:
A pigment dispersion according to the invention can be blended with a binder resin for paint and if necessary with such additives as organic solvent, polymer fine particles, curing catalyst, ultraviolet absorber, ultraviolet stabilizer, paint film surface regulating agent, antioxidant, flow property regulator and silan coupling agent, to form a pigment composition.
The binder resin for paint as referred to herein include substrate resins normally used in paint and combinations of such substrate resins with curing agents. Examples of substrate resins include hydroxyl-containing acrylic resin, hydroxyl-containing polyester resin, epoxy resin, epoxy-containing acrylic resin, carboxyl-containing high acid value polyester resin and carboxyl-containing high acid value acrylic resin, which can be used either singly or in combination. Examples of useful curing agent include amino resin and optionally blocked polyisocyanate resin.
As the binder resin for paint, combination of at least one substrate resin selected from hydroxyl-containing acrylic resins and hydroxyl-containing polyester resins with at least one curing agent selected from amino resins and optionally blocked polyisocyanate compounds; and combination of at least one resin selected from epoxy resins and epoxy-containing acrylic resins with at least one carboxyl-containing resin selected from high acid value ester resins and high acid value acrylic resins, can be conveniently used.
As organic solvent which may be used when necessity arises, various organic solvents such as those named as being useful in production of the copolymers can be used.
Said polymer fine particles are of a polymer which scatters as solid fine particles in the paint composition of the invention, not being dissolved. Such polymer fine particles are know per se, which conveniently possess an average particle size within a range of 0.01-1 mxcexc. While cross-linking inside said polymer fine particles is not essential, presence of internal crosslinkages is preferred.
As said curing catalyst, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, triethylamine and diethanolamine may be named, for example, where the curing agent is an optionally blocked polyisocyanate compound. Whereas, when an amino resin such as melamine resin is used as the curing agent, sulfonic acid compounds such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid and dinonylnaphthalenesulfonic acid or amine-neutralization products of these sulfonic acid compounds can be used.
Examples of the ultraviolet absorbing agents include benzophenone, benzotriazole, cyanoacrylate, salicylate and oxanilide compounds. Also as examples of ultraviolet stabilizer, hindered amine compounds can be named.
The paint compositions of the invention are usefil in the field where coloring paint is applied. They can be conveniently used, for example, as top coating and coloring paint in 1-top coat finishing; as coloring base paint in 2-top coat finishing consisting of coloring basexe2x80x94clear top coating (including both 2-coat-1-bake finish and 2-coat-2-bake finish); and as coloring base paint in 3-top coat finishing (including all of 3-coat-1-bake finish, 3-coat-2-bake finish and 3-coat-3-bake finish).